Two　pyrrolide-imine　chelating　Ni(II)　complexes　{[2-(2-CH3O-C6H4-NCH)C4H3N]2Ni　(2a)　and　[(Fc-NCH)]C4H3N]2Ni　(2b,　Fc　=　ferrocenyl)}　were　prepared　via　treating　corresponding　Schiff　base　with　0.5　equiv.　NiCl2·6H2O　in　moderate　yields.　The　crystal　structures　of　2a　and　2b　were　determined　by　single-crystal　X-ray　diffraction.　Atom　Ni(II)　of　2a　was　coordinated　by　two　pyrrolide-imine　ligands　in　trans　position　to　display　a　twisted　octahedral　coordination　geometry.　Ni(II)　of　2b　had　a　distorted　square-planar　geometry,　bonded　with　two　ferrocenyl　pyrrole-imine　ligands,　each　ferrocene　and　pyrrole　of　ligands　adopting　a　trans　conformation.　The　UV-vis　spectroscopy　and　electrochemical　measurements　were　investigated.　The　catalytic　efficiency　of　the　complexes　on　the　thermal　decomposition　of　ammonium　perchlorate　(AP)　was　studied　by　differential　scanning　calorimetry　(DSC)　and　thermogravimetry　(TG).　Compared　with　the　thermal　decomposition　of　pure　AP,　the　decomposition　temperatures　were　decreased　by　27　°C,　77°C,　88°C　and　172°C,　respectively　when　1a,　1b,　2a　and　2b　were　added　in　AP.　The　results　indicated　that　the　Ni(II)　complex　2b　bearing　ferrocene-based　pyrrolide-imine　N,N-chelate　ligand　displayed　an　excellent　catalytic　efficiency　on　the　thermal　decomposition　of　AP.　©　2014　Elsevier　B.V.　All　rights　reserved.